CN116874492A - 一种有机电致发光材料及其制备方法与应用 - Google Patents
一种有机电致发光材料及其制备方法与应用 Download PDFInfo
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- CN116874492A CN116874492A CN202310774104.7A CN202310774104A CN116874492A CN 116874492 A CN116874492 A CN 116874492A CN 202310774104 A CN202310774104 A CN 202310774104A CN 116874492 A CN116874492 A CN 116874492A
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- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于有机发光技术领域,涉及一种有机电致发光材料及其制备方法与应用。本发明公开的有机电致发光材料具有如说明书所述通式I所示结构。本发明公开了一种具有有机稠环的发光化合物,用于有机电致发光器件等光电器件后,可降低光电器件的驱动电压,显著提高光电器件的发光效率以及延长光电器件的的使用寿命;且,本发明提供的制备工艺具有合成步骤简单、易提纯及目标产物收率高的特点,适于推广与应用。
Description
技术领域
本发明属于有机发光材料技术领域,涉及一种有机电致发光材料及其制备方法与其在制备有机电致发光器件中的应用。
背景技术
1987年,邓青云博士发表了基于有机发光材料的电致发光二极管技术,这项技术得到了世界科研人员的广泛关注,有效的推动了有机电致发光技术在实用化应用方面的发展。
随着有机电致发光二极管技术的不断进步,有机电致发光器件由于具有自发光、广视角、对比度高、响应时间短、驱动电压低等特性,并可通过三种有机电致发光材料(红色,绿色和蓝色)来实现全色OLED显示器,是最具前景的新型显示技术,可用于平板显示器和照明光源,目前平板显示器已经实现规模产业化,各行业应用的产品已批量投入市场。
随着OLED产品不断的投入市场,人们对于此类产品的性能和稳定性的要求越来越高。当前已经应用的OLED材料和器件结构仍然无法完全解决OLED产品效率、寿命、成本等各方面的问题。为了满足人们对于OLED器件的更高要求,更符合未来生活需求的要求,开发合成多种发光效率高、驱动电压低的磷光发光材料,并且降低合成成本是本领域着重解决的问题。
发明内容
有鉴于此,本发明提供了一种有机电致发光材料及其制备方法和在有机电致发光器件中的应用。
为了实现上述目的,本发明的第一个目的在于提供一种有机电致发光材料。
采用如下技术方案:
所述有机电致发光材料的结构通式为通式I:
R选自-L-(A)n;
L选自取代或未取代的C6~C30芳基、取代或未取代的C6~C30杂芳基,其杂原子至少含有O、S、N、Si、Se中的一种;
n选自整数1或者2,且当n选自为2,每个A可以相同或不同;
A选自取代或未取代的C6~C30芳基、取代或未取代的C6~C30杂芳基,其杂原子至少含有O、S、N、Si、Se中的一种;取代或未取代的C6-C30的芳基胺基、取代或未取代的C6-C30的杂芳基胺基,其杂原子至少含有O、S、N、Si、Se中的一种;取代或非取代的C8~C30的稠环基。
可选地,所述C6~C30芳基为单环基团或多环基团;其中,多环基团具有两个碳为两个邻接环共用的多个环,至少一个环是芳香族环,其它环为环烷基、环烯基、芳基和芳族杂环基中的至少一种;
所述C6~C30杂芳基为呋喃、噻吩、吡啶、咔唑、吡嗪、嘧啶、三嗪、喹啉、异喹啉、喹喔啉、喹唑林、咪唑、苯并咪唑中的任一种。
可选地,L优选自苯、联苯、萘、菲、蒽、芴、苯并芴、二苯并芴、三亚苯、荧蒽、芘、苝、螺芴、二苯并呋喃、二苯并噻吩、吡啶、吡嗪、嘧啶、三嗪、喹啉、异喹啉、喹喔啉、喹唑林、咪唑、苯并咪唑、茚并芴或氢化的苯并蒽中的至少一种。
需要说明的是,上述的“取代”是指与化合物的碳原子键合的氢原子变成另外的取代基,并且取代的位置没有限制,只要该位置为氢原子被取代的位置即可,即取代基可以取代的位置,并且当两个或更多个取代基取代时,两个或更多个取代基可以彼此相同或不同。其中取代基为氘、卤素、氰基、C1~C30烷基、取代或非取代的C6~C30芳基、取代或非取代的C6~C30杂芳基、取代或非取代的C8~C30的稠环基。
优选地,所述化合物的化学结构式为式L001~式L308中的任一种:
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本发明的另一目的在于提供一种上述有机电致发光材料的制备方法,具体包括以下步骤:
(1)氮气保护下,将原料A(1.0eq)、原料B(1.0eq)、碘化亚铜(0.5eq)、邻菲罗啉(1.0eq)、氢氧化钾(3.0eq)、二甲苯(1000ml)加入反应瓶中,升温70℃反应,反应结束后冷却降温,经过柱层析提纯得到中间体化合物L-1;
(2)氮气保护下,将原料C(1.0eq)、原料D(4.0eq)、乙酸钾(2.0eq)加入反应瓶中,加入溶剂1,4-二氧六环(1000ml)、三(二亚苄基丙酮)二钯(0.01eq)和X-phos(0.08eq),升温100℃反应,反应结束降温至室温,经过柱层析提纯得到中间体化合物L-2;
(3)氮气保护下,将化合物L-1(1.0eq)、化合物L-2(1.0eq)、碳酸钾(2.0eq)、四(三苯基膦)钯(0.01eq)、甲苯(400ml)、乙醇(200ml)、水(200ml)加入到反应瓶中,升温90℃反应,反应结束后冷却至室温,经过柱层析提纯得到中间体L;
(4)氮气保护下,将中间体L(1.0eq)、原料E(1.1eq)与叔丁醇钠(1.5eq)混合后,加入溶剂甲苯(400ml)中,加入三(二亚苄基丙酮)双钯(0.01eq)、三叔丁基膦(0.02eq),加热升温至120℃反应,反应结束后经过柱层析提纯、旋蒸浓缩,得到通式I。
本发明的另一目的在于提供一种上述有机电致发光材料在制备有机电致发光器件中的应用。
所述的有机电致发光器件包括第一电极、第二电极以及至少一层设置在所述第一电极和所述第二电极之间的有机物层,所述的有机物层包含上述的有机电致发光材料。
优选的,所述有机物层包括发光层;所述发光层包括主体材料和掺杂材料;所述主体材料部分或全部包含所述的有机电致发光材料。
此外,有机物层还可以包括其它功能层,其它功能层具体可选自以下功能层中的一种或几种:空穴注入层(HIL)、空穴传输层(HTL)、空穴注入-空穴传输功能层(即兼具空穴注入及空穴传输功能)、电子阻挡层(EBL)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)、电子传输-电子注入功能层(即兼具电子传输及电子注入功能)。
上述各个功能层的种类没有特殊限制,为本领域技术人员熟知的常规功能层即可。
第一电极作为阳极,阳极优选包含具有高逸出功的材料。例如Ag、Pt或Au。优选的阳极材料在此是导电混合金属氧化物。特别优选的是氧化锡铟(ITO)或氧化铟锌(IZO)。此外优选的是导电的掺杂有机材料,特别是导电的掺杂聚合物。由于在水和/或空气存在下本发明器件的寿命会缩短,所以所述器件被适当地(取决于应用)结构化、提供接点并最后密封。
空穴传输材料是能够接收来自阳极或空穴注入层的空穴并将空穴传输至发光层的材料,并且具有高空穴迁移率的材料。其具体实例包括基于芳基胺的有机材料、导电聚合物、同时具有共轭部分和非共轭部分的嵌段共聚物等,但不限于此。
发光层的材料是一种通过分别接收来自空穴传输层和电子传输层的空穴和电子,并将所接收的空穴和电子结合而能发出可见光的材料。
优选的,所述主体材料和掺杂材料的质量比为(90~99.5):(0.5~10)。
掺杂材料可以包括荧光掺杂材料和磷光掺杂材料。磷光掺杂材料的包括铱、铂等的金属络合物的磷光材料。例如,可以使用Ir(ppy)3等绿色磷光材料,FIrpic、FIr6等蓝色磷光材料和Btp2Ir(acac)等红色磷光材料。
具体的,掺杂材料可以采用在欧洲专利申请07102949.0的化合物作为发光层中的掺杂剂。
电子阻挡层可以设置在空穴传输层与发光层之间。作为电子阻挡层,可以使用本领域中已知的材料,例如基于芳基胺的有机材料。
空穴阻挡层材料,可以使用现有技术中公知的具有空穴阻挡作用的化合物,例如,浴铜灵(BCP)等菲咯啉衍生物、噁唑衍生物、三唑衍生物、三嗪衍生物等,但不限于此。
电子传输层可以起到促进电子传输的作用。电子传输材料是有利地接收来自阴极的电子并将电子传输至发光层的材料,具有高电子迁移率的材料是合适的。作为本发明有机电致发光器件的电子传输层材料,可以使用现有技术中公知的具有电子传输作用的化合物,例如,8-羟基喹啉的Al配合物;包含Alq3的配合物;有机自由基化合物;羟基黄酮-金属配合物等等,但不限于此。
电子注入层可以起到促进电子注入的作用。具有传输电子的能力,防止发光层中产生的激子迁移至空穴注入层。本发明中使用的电子注入材料包括芴酮、蒽醌二甲烷、联苯醌、噻喃二氧化物、唑、二唑、三唑、咪唑、苝四羧酸、亚芴基甲烷、蒽酮等及其衍生物,金属配合物,含氮五元环衍生物等,但不限于此。
第二电极作为阴极,通常优选具有小功函数的材料使得电子顺利注入有机材料层。包括:金属,例如镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡和铅,或其合金;多层结构材料,例如LiF/Al或LiO2/Al,该层的层厚度优选在0.5和5nm之间。
在本发明实施例中,可通过溶液涂覆法和真空沉积法的方式形成上述各种功能层。溶液涂覆法意指旋涂、浸涂、喷墨印刷、丝网印刷、喷洒法等,但不限于此。
另外,上述的有机电致发光器件可以为有机电致发光器件、有机太阳电池、电子纸、有机感光体或有机薄膜晶体管等,但不限于此。
与现有技术相比,本发明的有益效果是:
1)本发明提供的一种具有有机稠环的发光化合物,用于有机电致发光器件等光电器件后,可降低光电器件的驱动电压,显著提高光电器件的发光效率以及延长光电器件的的使用寿命。
2)本发明提供的发光化合物的制备方法,具有合成步骤简单、易提纯及目标产物收率高的特点,适于推广与应用。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本说明书中各个实施例采用递进的方式描述,每个实施例重点说明的都是与其他实施例的不同之处,各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言,由于其与实施例公开的方法相对应,所以描述的比较简单,相关之处参见方法部分说明即可。
化合物实施例1
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L001,该发光化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取原料A(406.32mmol,100g)(CAS:16807-11-7),原料B(406.32mmol,114.95g)(CAS:583-55-1),碘化亚铜(203.16mmol,38.69g)、邻菲罗啉(406.32mmol,73.22g)、氢氧化钾(1218.97mmol,68.39g)、放入反应体系中,接着,往反应体系中加入1000mL甲苯,使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到中间体化合物L-1(90.58g,产率:55.58%)。
1HNMR(500MHz,Chloroform-d)δ8.12–8.06(m,1H),8.01(dd,J=7.3,1.6Hz,1H),7.65–7.59(m,1H),7.57(dd,J=7.5,1.5Hz,1H),7.47(dd,J=7.5,1.7Hz,1H),7.42(t,J=7.4Hz,1H),7.38(dd,J=7.4,1.6Hz,1H),7.36–7.28(m,3H),7.16(td,J=7.5,1.6Hz,1H).
在氮气保护体系下,称取原料C(307.69mmol,100g)(CAS:905702-33-2),原料D(615.39mmol,156.27g)(CAS:73183-34-3),乙酸钾(769.23mmol,75.49g)、三(二亚苄基丙酮)二钯(3.08mmol,2.82g)、X-phos(24.62mmol,11.73g)、放入反应体系中,接着,往反应体系中加入1000mL 1,4-二氧六环,使反应体系在氮气保护下100℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到中间体化合物L-2(60.17g,产率:46.66%)。
1HNMR(500MHz,Chloroform-d)δ9.98(s,1H),δ7.45(dd,J=7.4,1.6Hz,2H),7.30(dd,J=7.5,1.6Hz,2H),7.21(s,2H),1.24(s,24H).
在氮气保护体系下,称取化合物L-1(149.59mmol,60g),L-2(149.59mmol,62.70g),碳酸钾(299.18mmol,41.29g)放入反应体系中,接着,往反应体系中加入500mL甲苯、250mL乙醇、250mL纯净水、四(三苯基膦)钯(1.20mmol,1.73g),使反应体系在氮气保护下90℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到中间体化合物L001-1(32.73g,产率为53.83%);
1HNMR(500MHz,Chloroform-d)δ9.78(s,1H),8.17–8.04(m,1H),7.99(ddd,J=9.2,7.4,1.6Hz,2H),7.71(ddd,J=7.5,3.8,1.6Hz,2H),7.66–7.53(m,3H),7.48(t,J=7.5Hz,1H),7.41(td,J=7.5,1.6Hz,1H),7.37–7.21(m,7H).
在氮气保护体系下,称取化合物L001-1(49.20mmol,20g),L001-2(54.12mmol,16.90g)(CAS:80984-79-8),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L001(21.37g,产率:68.10%)。
HPLC纯度:大于99%;
质谱:测试值为638.17;
元素分析:
计算值C:84.75%;H:4.27%;N:10.98%;
测试值C:83.69%;H:3.88%;N:11.59%;
1HNMR(500MHz,Chloroform-d)δ8.59–8.52(m,4H),8.15–8.07(m,1H),8.02(dd,J=7.5,1.6Hz,1H),7.87–7.78(m,2H),7.70–7.58(m,6H),7.49–7.40(m,8H),7.37–7.29(m,5H).化合物实施例2
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L021,该化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L021-1(49.20mmol,20g),L021-2(54.12mmol,19.36g)(CAS:1472729-25-1),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L021(22.54g,产率:62.94%)。
HPLC纯度:大于99%;
质谱:测试值为728.24;
元素分析:
计算值C:84.16%;H:4.02%;N:9.62%;O:2.20%;
测试值C:83.09%;H:4.10%;N:9.98%;O:2.76%;
1HNMR(500MHz,Chloroform-d)δ8.59–8.53(m,2H),8.13–8.08(m,1H),8.02(ddd,J=8.2,6.6,1.5Hz,3H),7.89–7.79(m,3H),7.70–7.53(m,8H),7.50–7.36(m,8H),7.36–7.28(m,4H).
化合物实施例3
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L065,该化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L065-1(104.48mmol,30g)(CAS:854952-58-2),L065-2(104.48mmol,32.91g)(CAS:1973-01-9),碳酸钾(208.97mmol,28.84g)放入反应体系中,接着,往反应体系中加入200mL甲苯、100mL乙醇、100mL纯净水、四(三苯基膦)钯(1.05mmol,1.21g),使反应体系在氮气保护下70℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到中间体化合物L065-3(23.5g,产率为47.12%);
1HNMR(500MHz,Chloroform-d)δ9.34(d,J=1.4Hz,1H),8.59–8.53(m,2H),8.21(d,J=7.5Hz,1H),8.18–8.14(m,1H),8.08(dd,J=7.5,1.5Hz,1H),7.63–7.57(m,1H),7.55–7.42(m,7H),7.38–7.28(m,3H).
在氮气保护体系下,称取化合物L065-4(49.20mmol,20g),L065-3(54.12mmol,25.84g),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L065(25.83g,产率:65.38%)。
HPLC纯度:大于99%;
质谱:测试值为803.15;
元素分析:
计算值C:85.26%;H:4.27%;N:10.47%;
测试值C:84.20%;H:4.73%;N:11.01%;
1HNMR(500MHz,Chloroform-d)δ9.31(d,J=1.5Hz,1H),8.59–8.50(m,2H),8.23–8.14(m,2H),8.09(ddd,J=18.3,7.3,1.6Hz,2H),8.02(dd,J=7.5,1.6Hz,1H),7.83(ddd,J=13.3,7.5,1.5Hz,2H),7.69–7.58(m,5H),7.56(dd,J=7.5,1.5Hz,2H),7.53–7.36(m,10H),7.36–7.24(m,7H).
化合物实施例4
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L082,该化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L082-1(49.20mmol,20g),L082-2(54.12mmol,13.02g)(CAS:7065-92-1),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L082(15.97g,产率:53.15%)。
HPLC纯度:大于99%;
质谱:测试值为611.22;
元素分析:
计算值C:86.53%;H:4.29%;N:9.17%;
测试值C:85.10%;H:4.80%;N:10.04%;
1HNMR(500MHz,Chloroform-d)δ8.12(dd,J=7.3,1.6Hz,1H),8.02(td,J=7.7,1.7Hz,2H),7.99–7.93(m,1H),7.86–7.82(m,1H),7.81–7.74(m,3H),7.68–7.53(m,8H),7.46–7.38(m,5H),7.37–7.26(m,5H).
化合物实施例5
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L085,该化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L085-1(49.20mmol,20g),L085-2(54.12mmol,15.33g)(CAS:59951-65-4),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L085(21.12g,产率:70.52%)。
HPLC纯度:大于99%;
质谱:测试值为609.34;
元素分析:
计算值C:90.76%;H:4.64%;N:4.60%;
测试值C:88.90%;H:5.38%;N:5.63%;
1HNMR(500MHz,Chloroform-d)δ8.12(dd,J=7.1,1.9Hz,1H),8.02(dt,J=7.5,1.5Hz,2H),7.89(dd,J=7.5,1.7Hz,1H),7.84(dd,J=6.9,2.2Hz,1H),7.75(dd,J=7.5,1.5Hz,1H),7.66–7.56(m,7H),7.53(ddd,J=7.9,6.5,1.6Hz,2H),7.48–7.39(m,5H),7.39–7.27(m,7H),7.21(t,J=7.5Hz,1H).
化合物实施例6
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L097,该化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L097-1(159.90mmol,60g)(CAS:148231-12-3),L097-2(159.90mmol,46.04g)(CAS:100124-06-9),碳酸钾(319.80mmol,44.13g)放入反应体系中,接着,往反应体系中加入200mL甲苯、100mL乙醇、100mL纯净水、四(三苯基膦)钯(1.60mmol,1.85g),使反应体系在氮气保护下70℃回流反应24小时,反应停止后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到中间体化合物L097-3(25.60g,产率为42.67%);
1HNMR(500MHz,Chloroform-d)δ8.79–8.61(m,2H),8.11–7.94(m,3H),7.90–7.81(m,2H),7.58(dd,J=7.5,1.6Hz,1H),7.54–7.42(m,2H),7.36(td,J=7.5,1.6Hz,1H).
在氮气保护体系下,称取化合物L097-4(49.20mmol,20g),L097-3(54.12mmol,20.31g),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L097(22.54g,产率:65.44%)。
HPLC纯度:大于99%;
HPLC纯度:大于99%;
质谱:测试值为701.04;
元素分析:
计算值C:85.69%;H:4.03%;N:7.99%;O:2.28%;
测试值C:84.73%;H:4.32%;N:8.45%;O:2.45%;
1HNMR(500MHz,Chloroform-d)δ8.61(d,J=7.5Hz,1H),8.54(d,J=7.5Hz,1H),8.18(d,J=7.5Hz,1H),8.14–8.08(m,1H),8.08–7.97(m,4H),7.85(ddd,J=9.8,7.4,1.5Hz,2H),7.74(dd,J=7.5,1.6Hz,1H),7.69–7.50(m,8H),7.49–7.28(m,8H),7.25(t,J=7.5Hz,1H).
化合物实施例7
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L109,该化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L109-1(49.20mmol,20g),L109-2(54.12mmol,17.55g)(CAS:36809-26-4),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L109(26.74g,产率:83.64%)。
HPLC纯度:大于99%;
质谱:测试值为649.48;
元素分析:
计算值C:88.72%;H:4.81%;N:6.47%;
测试值C:87.38%;H:5.23%;N:7.24%;
1HNMR(500MHz,Chloroform-d)δ8.15–8.08(m,1H),8.02(dd,J=7.5,1.6Hz,1H),7.86–7.80(m,1H),7.73(dd,J=7.5,1.5Hz,1H),7.67–7.62(m,2H),7.62–7.55(m,4H),7.49–7.44(m,2H),7.43(d,J=7.5Hz,1H),7.38–7.23(m,9H),7.23–7.16(m,3H),7.15–7.07(m,6H).化合物实施例8
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L111,该化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L111-1(49.20mmol,20g),L111-2(54.12mmol,21.67g)(CAS:503299-24-9),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L111(23.48g,产率:65.74%)。
HPLC纯度:大于99%;
质谱:测试值为726.81;
元素分析:
计算值C:89.35%;H:4.86%;N:5.79%;
测试值C:88.50%;H:5.12%;N:6.35%;
1HNMR(500MHz,Chloroform-d)δ8.14–8.06(m,1H),8.02(dd,J=7.6,1.5Hz,1H),7.84(dd,J=7.5,1.5Hz,1H),7.72(dd,J=7.5,1.5Hz,1H),7.66–7.50(m,10H),7.50–7.23(m,13H),7.19(ddt,J=7.8,6.9,1.5Hz,5H),7.13–7.03(m,3H).
化合物实施例9
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L173,该化合物的制备方法的反应路线如下:
在氮气保护体系下,称取化合物L173-1(99.44mmol,40g)(CAS:2244026-60-4),L173-2(99.44mmol,27.45g)(CAS:3900-89-8),碳酸钾(198.88mmol,27.44g)放入反应体系中,接着,往反应体系中加入200mL甲苯、100mL乙醇、100mL纯净水、四(三苯基膦)钯(1.60mmol,1.85g),使反应体系在氮气保护下70℃回流反应24小时,反应停止后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到中间体化合物L173-3(22.10g,产率为51.22%,Mw:433.90);
1HNMR(500MHz,Chloroform-d)δ8.59–8.53(m,2H),8.03(ddd,J=12.3,7.4,1.5Hz,2H),7.94(dd,J=7.5,1.5Hz,1H),7.82–7.76(m,1H),7.61–7.54(m,2H),7.54–7.40(m,7H),7.37(td,J=7.4,1.7Hz,1H).
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L173-4(49.20mmol,20g),L173-3(54.12mmol,23.48g),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L173(19.56g,产率:49.45%)。
HPLC纯度:大于99%;
质谱:测试值为804.71;
元素分析:
计算值C:85.16%;H:4.14%;N:8.71%;O:1.99%;
测试值C:84.33%;H:4.56%;N:8.98%;O:2.11%;
1HNMR(500MHz,Chloroform-d)δ8.60–8.50(m,2H),8.11(dd,J=7.1,1.9Hz,1H),8.05–7.98(m,3H),7.94–7.87(m,2H),7.84(dd,J=7.5,1.5Hz,1H),7.74(dd,J=7.5,1.5Hz,1H),7.68–7.52(m,9H),7.52–7.36(m,9H),7.37–7.25(m,4H),7.21(t,J=7.4Hz,1H).
化合物实施例10
该化合物实施例提供了一种化合物,其化学结构式为发明内容中的式L212,该化合物的制备方法的反应路线如下:
其具体的制备方法包括以下步骤:
在氮气保护体系下,称取化合物L212-1(49.20mmol,20g),L212-2(54.12mmol,13.92g)(CAS:1564-64-3),叔丁醇钠(73.80mmol,7.09g)放入反应体系中,接着,往反应体系中加入200mL甲苯,三(二亚苄基丙酮)双钯(0.49mmol,0.45g)和50%三叔丁基膦(0.98mmol,0.40g)使反应体系在氮气保护下120℃回流反应24小时,反应结束后体系冷却至室温,经过硅胶柱柱层析提纯,滤液浓缩固体析出,得到最终化合物L212(20.44g,产率:71.29%)。
HPLC纯度:大于99%;
质谱:测试值为583.61;
元素分析:
计算值C:90.69%;H:4.50%;N:4.81%;
测试值C:89.88%;H:4.74%;N:5.29%;
1HNMR(500MHz,Chloroform-d)δ8.33(dd,J=7.4,1.6Hz,2H),8.25(t,J=1.7Hz,1H),8.12(dd,J=7.1,1.8Hz,1H),8.02(dd,J=7.5,1.6Hz,1H),7.92(dt,J=7.5,1.7Hz,2H),7.84(dd,J=7.5,1.5Hz,1H),7.76(dd,J=7.5,1.5Hz,1H),7.70–7.55(m,6H),7.49(td,J=7.5,1.5Hz,2H),7.46–7.36(m,4H),7.37–7.28(m,4H),7.24(t,J=7.5Hz,1H).
照化合物实施例1至10的制备方法进行,将化合物L和化合物D分别替换为目标产物中的相应化合物,从而得到下述一系列化合物,参见下表1。按照化合物实施例1~10中的检测方法对各产物进行检测分析,其质谱和分子式如表1所示。
表1
其余未列明具体合成方法的化合物,可以参照以上实施例,采用本领域现有的合成方法进行合成。
本发明实施例还提供了一种采用上述实施例提供的发光化合物制备得到的有机电致发光器件,其中有机电致发光器件包括:第一电极、第二电极和置于所述两电极之间的一个或者更多个有机物层,其中,所述有机物层的一个或更多个层包含有本发明化学式I所示的化合物;本发明化学式I所示化合物可以是单一形态或与其它物质混合存在于有机物层中;
有机物层至少包括空穴注入层、空穴传输层、既具备空穴注入又具备空穴传输技能层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层和既具备电子传输又具备电子注入技能层中的一种或几种。
为了更进一步的描述本发明,以下列举更具体的器件实施例。
器件实施例1
有机电致发光器件的结构为:ITO/NPB(20nm)/红光主体材料:Ir(piq)3[10%](35nm)/TPBI(10nm)/Alq3(15nm)/LiF(0.5nm)/Al(150nm)。其中“Ir(piq)3[10%]”是指红光掺杂材料的掺杂比例,即红光主体材料与Ir(piq)3的重量份比为100:10。
有机电致发光器件制备过程如下:
将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理,在去离子水中冲洗,在丙酮:乙醇混合溶剂中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光和臭氧清洗,并用低能阳离子束轰击表面。
把上述带有阳极的玻璃基片置于真空腔内,抽真空至1×10-5~9×10-3Pa,在上述阳极层膜上真空蒸镀空穴传输层NPB,蒸镀速率为0.1nm/s,蒸镀膜厚为20nm。
在空穴传输层之上真空蒸镀红光主体材料L001和掺杂材料Ir(piq)3,作为有机电致发光器件的发光层,蒸镀速率为0.1nm/s,蒸镀总膜厚为35nm;
在发光层之上依次真空蒸镀电子传输层TPBI和Alq3,其蒸镀速率均为0.1nm/s,蒸镀膜厚分别为10nm和15nm。
在电子传输层上真空蒸镀0.5nm的LiF,150nm的Al作为电子注入层和阴极。
所有有机电致发光器件均采用上述方法制备得到,区别仅在于红光主体材料的选择。
测量了所制备有机电致发光器件的亮度、驱动电压、电流效率以及寿命测试T95。其中,寿命测试T95是指在室温(25~27℃),保持初始亮度下的电流密度不变(此处为1000cd/m2),亮度降低为初始亮度95%所需要的时间。
器件实施例2~器件实施例20
参照上述器件实施例1提供的制备方法,将器件实施例1中使用的发光化合物L001分别替换为上述实施例提供的式L011、L021、L025、L037、L065、L074、L082、L085、L097、L101、L109、L111、L155、L167、L173、L188、L191、L203、L212所示的发光化合物作为主体材料与掺杂材料进行混合蒸镀,并制备得到相应的有机电致发光器件。
器件对比例1
该器件对比例制造了一种有机电致发光器件。具体的,按照器件实施例1的制备方法,将器件实施例1中使用的化合物L001替换为D-1、D-2作为主体材料与掺杂材料进行混合蒸镀,并制备得到相应的有机电致发光器件。其中,D-1、D-2的结构式为:
在亮度为1000cd/m2的条件下对上述器件实施例1~20以及器件对比例1、2得到的有机电致发光器件进行发光性能检测,采用KEITHLEY 2400型测量单元,CS-2000分光辐射亮度计,测试驱动电压、寿命及发光效率,其测试结果参见表2:
表2
从表2可以看出,将本发明实施例提供的化合物作为有机电致发光器件的发光层的主体材料,相比于现有使用的主体材料,可以显著地降低有机电致发光器件的驱动电压以及提高有机电致发光器件的发光效率和使用寿命。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (7)
1.一种有机电致发光材料,其特征在于,具有通式I所示结构:
R选自-L-(A)n;
L选自取代或未取代的C6~C30芳基、取代或未取代的C6~C30杂芳基,其杂原子至少含有O、S、N、Si、Se中的一种;
n选自整数1或者2,且当n选自为2,每个A可以相同或不同;
A选自取代或未取代的C6~C30芳基、取代或未取代的C6~C30杂芳基,其杂原子至少含有O、S、N、Si、Se中的一种;取代或未取代的C6-C30的芳基胺基、取代或未取代的C6-C30的杂芳基胺基,其杂原子至少含有O、S、N、Si、Se中的一种;取代或非取代的C8~C30的稠环基。
2.根据权利要求1所述的有机电致发光材料,其特征在于,所述C6~C30芳基为单环基团或多环基团;其中,多环基团具有两个碳为两个邻接环共用的多个环,至少一个环是芳香族环,其它环为环烷基、环烯基、芳基和芳族杂环基中的至少一种;
所述C6~C30杂芳基为呋喃、噻吩、吡啶、咔唑、吡嗪、嘧啶、三嗪、喹啉、异喹啉、喹喔啉、喹唑林、咪唑、苯并咪唑中的任一种。
3.根据权利要求1所述的有机电致发光材料,其特征在于,L优选自苯、联苯、萘、菲、蒽、芴、苯并芴、二苯并芴、三亚苯、荧蒽、芘、苝、螺芴、二苯并呋喃、二苯并噻吩、吡啶、吡嗪、嘧啶、三嗪、喹啉、异喹啉、喹喔啉、喹唑林、咪唑、苯并咪唑、茚并芴或氢化的苯并蒽中的至少一种。
4.根据权利要求1所述的有机电致发光材料,其特征在于,所述有机电致发光材料选自以下结构:
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5.一种如权利要求1所述有机电致发光材料的制备方法,其特征在于,所述方法具体包括如下步骤:
(1)氮气保护下,将原料A(1.0eq)、原料B(1.0eq)、碘化亚铜(0.5eq)、邻菲罗啉(1.0eq)、氢氧化钾(3.0eq)、二甲苯(1000ml)加入反应瓶中,升温70℃反应,反应结束后冷却降温,经过柱层析提纯得到中间体化合物L-1;
(2)氮气保护下,将原料C(1.0eq)、原料D(4.0eq)、乙酸钾(2.0eq)加入反应瓶中,加入溶剂1,4-二氧六环(1000ml)、三(二亚苄基丙酮)二钯(0.01eq)和X-phos(0.08eq),升温100℃反应,反应结束降温至室温,经过柱层析提纯得到中间体化合物L-2;
(3)氮气保护下,将化合物L-1(1.0eq)、化合物L-2(1.0eq)、碳酸钾(2.0eq)、四(三苯基膦)钯(0.01eq)、甲苯(400ml)、乙醇(200ml)、水(200ml)加入到反应瓶中,升温90℃反应,反应结束后冷却至室温经过柱层析提纯得到中间体L;
(4)氮气保护下,将中间体L(1.0eq)、原料E(1.1eq)与叔丁醇钠(1.5eq)混合后,加入溶剂甲苯(400ml)中,加入三(二亚苄基丙酮)双钯(0.01eq)、三叔丁基膦(0.02eq),加热升温至120℃反应,反应结束后经过柱层析提纯、旋蒸浓缩,得到通式I;
具体合成路线如下:
6.一种如权利要求1所述有机电致发光材料或如权利要求5所述方法制备的有机电致发光材料在有机电致发光器件中的应用。
7.根据权利要求6所述的应用,其特征在于,所述有机电致发光器件,包括第一电极、第二电极以及至少一层设置在所述第一电极和所述第二电极之间的有机物层;其中,
所述有机物层包含所述的有机电致发光材料。
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